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Change of pH has been identified as the most significant parameter in modulating the transition between the conversions of acids into solvents in acetone-butanol-ethanol (ABE) fermentation by Clostridia. Thus, ABE fermentation at various phosphate buffer concentrations and initial pH values was conducted using pure glucose and sugars derived from pretreated oil palm empty fruit bunch (OPEFB). A higher solvent concentration (2.93 g/L) was obtained in the fermentation using 20 g/L of glucose with buffer compared with one without buffer that produced 1.34 g/L of solvents. Approximately 8.77 and 9.15 g/L of solvents were produced from fermentation using 40 g/L of glucose with and without buffer, respectively. In the latter conditions, at an initial pH of 5.5, 8.77 g/L of solvents was obtained, which was the highest concentration compared to other initial pH values. Increasing the buffer concentration to 0.2 M at an initial pH of 6.0 resulted in acid accumulation of 16.83 g/L but reduced the solvent production to 1.36 g/L. In addition, ABE fermentation using 20 g/L of sugars from pretreated OPEFB produced 2.25 g/L of solvents with a yield of 0.13 g/g, which was comparable with fermentation using 20 g/L of glucose conducted in a buffering system.